Compositions comprising boron compounds and polyphenyl thioethers

ABSTRACT

Compositions comprising polyphenyl thioethers, polyphenylethers - thioethers or mixtures thereof and phenylboric acids and/or diphenylborinic acids exhibit improved corrosiveness toward copper and silver without loss of oxidative stability. Such compositions are useful as functional fluids.

United ttes atet 1 Clark et al. Aug. 28, 1973 [54] COMPQSITIONS COMPRISING BORON 3,092,652 6/1963 Stern et a1 260/462 R COMPOUNDS AND pOLYPHENYL 3,108,966 10/1963 Dadura et al..... 252/46.3 THHOETHERS 3,129,249 4/1964 Koster 260/6065 B 3,518,314 6/1970 Gieseking 252/78 X [75] Inventors: Frank S. Clark; Loren W. Bannister, 3.538.166 11/1970 Campbell et a1 252/78 X OTHER PUBLICATIONS Assignee: M n n mp ny, L i M Chemical Abstracts Vol. 56, 12918(d) (1962) 22 F] d: l 9, 1971 1 16 y 2 Primary Examiner-Leon D. Rosdol PP ,462 Assistant Examinerl larris A. Pitlick Attorney-Neal E. Willis et al. [52] US. Cl 252/78, 252/46.3, 252/49.6,

252/389 R, 260/462 A [571 ABSTRACT [51] Int. Cl C09k 3/00 Compositions comprising polyphenyl thioethers, poly- [58] Field of Search 252/75, 78, 389, phenylethers thioethers or mixtures thereof and phe- 252/49.6, 46.3; 260/462 A nylboric acids and/or diphenylborinic acids exhibit improved corrosiveness toward copper and silver without [56] References Cited loss of oxidative stability. Such compositions are useful UNlTED STATES PATENTS as functional flulds- 2,312,208 2/ 1943 Clayton et a1. 252/75 15 Claims, No Drawings COMPOSKTIONS COMPRISING BORON COMPOUNDS AND POLYPHENYL THIOETHERS This invention relates to compositions comprising polyphenyl thioethers, polyphenyl ethers-thioethers or mixtures thereof, containing from 3 to 8 aromatic groups and a corrosion inhibiting amount of phenylboric acids, diphenylborinic acids or admixtures thereof. The compositions of this invention are useful as functional fluids.

Polyphenyl thioethers and polyphenyl etherthioether combinations have found wide application as functional fluids due to their excellent thermal stability and lubricity. For example they have been found to be valuable as hydraulic fluids and as lubricants in .motor operation, particularly in jet engines, and as heat transfer agents. Two of the most rigorous demands on fluids are made by jet aircraft hydraulic systems and jet engine lubrication systems. For example, as the speedand altitude of operation of jet powered aircraft increases, lubrication problems also increase because of higher operating temperatures and higher .bearing pressures resulting from the increased thrust needed to obtain higher speeds and altitudes. Thus, the service conditions encountered by functional fluids become increas ingly severe, and therefore, the useful life of such fluids is shortened.

The useful life of any lubricant or hydraulic fluid can be adjudged on the basis of many criteria such as the extent of viscosity increase, the extent of corrosion to metal surfaces in contact with the lubricant and the extent of engine deposits. Those skilled in the art have found various ways to improve lubricants and to thus retard or prevent the effects which shorten the useful life of a lubricant. Thus, for example, small amounts of other materials, or additives, can .be added to lubricants in order to affect one or more of the properties of the base lubricant. However, it is difficult, especially as operating temperatures are increased, to find additives which will still perform the function for which they are added and yet not inject other problems.

Therefore, an object of this invention is to extend the useful life of polyphenyl thioethers, polyphenyl etherthioethers or mixtures thereof by reducing their corrosivity toward certain metals without adversely affecting oxidative stability of the ethers.

These and other objects will become evident upon consideration of the following specification and examples.

The above and other object of this invention are carried out by admixing polyphenyl thioethers, polyphenyl ether-thioethers or mixtures thereof with a corrosion inhibiting amount of phenylboric acids, diphenylborinic acids or admixtures thereof. The ether-boron compositions of this invention exhibit reduced corrosiveness toward metals without an adverse effect on oxidative stability of the base ether and thus have an extended service life even under the severe conditions encountered in jet engines and other devices operating at temperatures of the order of 600"F. The compositions exhibit markedly reduced corrosion toward copper and silver.

The improved compositions of this invention com.- prise a major amount of an ether base fluid of the formula wherein R is phenyl,alkyl-substituted phenyl wherein the alkyl is of not more than four carbon atoms, alkoxysubstituted phenyl wherein the alkoxy is of not more than four carbon atoms or halogenated phenyl wherein the halogen is bromine, fluorine or chlorine, R is phenylene, alkyl or alkoxy-substituted phenylene wherein the alkyl contains no more than four carbon atoms or halogenated phenylene wherein the halogen is fluorine, bromine or chlorine, and Y is selected from oxygen and sulfur but at least one of the Ys issulfur and a is an integer having a value of l to 6 and a corrosion inhibiting amount of a boron compound of the formula Wherein R is alkyl of not more than four carbon atoms, halogen (Cl, Br and F) alkoxy of not more than four carbon atoms, haloalkyl of not more than four carbon atoms and 3 halogen atoms (Cl, Brzand F) haloalkoxy of not 'more than four carbon atoms and 3 halogen atoms (Cl, Br and F), phenoxy, phenylmercapto or N0 R" is halogen (Cl, Br and F) or alkyl of not more than four carbon atoms, n is an integer of O to 3, m is an integer of 0 to 2, x and y are integers from 1 to 2 and the sum of x and y is 3.

Representative groups for R in the-above formula inelude halogen (Cl, Br and F), N0 phenoxy, thiophenoxy, alkyl such as methyl, ethyl; propyl, isopropyl, n-butyl, secbutyl and t-butyl, alkoxysuch as methoxy, ethoxy, butoxy, haloalkyl such as chloromethyl, bromomethyl, chloroethyl, bromoethyl, trichloromethyl, tribromomethyl, trifluoroethyl, dichloroethyl, chloro-n-propyl, bromo-n-propyl, bromo-n-butyl, bromo-tert-butyl, l,3,3,-trichlorobutyl and 1,3,3,- tribromobutyl and haloalkoxy such as chloromethoxy, l,2-dichlorobutoxy and fluoropropoxy. Representative groups for R include the halogen and alkyl listed above for R.

Representative boron compounds of the above formula include phenylboric acid 4-methylphenylboric acid 2,4-dimethylphenylboric acid 4-n-butylphenylboric acid 4-methoxyphenylboric acid 2-chlorophenylboric acid Z-fluordphenylboric acid 4-chlorophenylboric acid 2,4-dichlorophenylboric acid 4-chloromethoxyphenylboric acid 4-phenoxyphenylboric acid 4-nitrophenylboric acid 4-phenylmercaptophenylboric acid 2-chloro-4-methylphenylboric acid 2-chloromethylphenylboric acid 3-methyl4-chlorophenylboric acid 2-chloro-4-phenoxyphenylboric acid diphenylborinic acid ditolylborinic acid The amount of boron compound employed in the compositions of this invention can range from about 0.01 to about 1.5 percent by weight. It is preferred to employ the acids in the compositions of this invention in amounts of from about 0.05 to about 1.5 percent by weight based upon the total composition.

The polyphenyl thioethers employed in the composition of this invention have from 3 to 8 benzene rings and from 1 to 7 sulfur atoms with the sulfur atomsjoining the benzene rings in chains as ether linkages.

The term polyphenyl thioether as used herein means a compound or physical mixture of compounds wherein all of the ys in the above formula are sulfur. The term "polyphenylether-thioether as used herein means compounds or physical mixtures of compounds wherein at least one but not all of the ys in the above formula is sulfur.

The compositions of this invention contain a major amount of the polyphenyl thioether or polyphenylether-thioether base stock, i.e., at least 50 percent by weight of the total composition comprises an ether. It is preferred that at least 60 percent by weight of the composition be an ether base stock and even more preferred that at least 85 percent by weight of the total composition comprise an ether.

Illustrations of the alkyl-substituents present in the phenyl and phenylene groups of the ethers are for example, methyl, ethyl, propyl, butyl and the like. Illustrations of the alkoxy-substituents are, for example, methoxy, ethoxy, propoxy, butoxy and their isomers.

The compositions of this invention can also contain from 0.01 to 10 percent by weight of the total composition of a dialkyl hydrogen phosphite extreme pressure additive. The dialkyl hydrogen phosphites useful are those wherein the alkyl groups contain from one to 12 carbon atoms. The alkyl groups are 'for example, methyl, ethyl propyl, isopropyl, butyl, secbutyl, t-butyl, hexyl, decyl, isodecyl, dodecyl and the like.

Illustrative of the polyphenyl thioethers which can be employed as base'stocks for the compositions of this invention are the bis(phenylmercapto)benzenes. For example m-bis(phenylmercapto)benzene o-bis(phenylmercapto)benzene p-bis(phenylmercapto)benzene bis(m-phenylmercaptophenyl)sulfide bis(o-phenylmercaptophenyl)sulfide bis(p-phenylmercaptophenyl)sulfide (m-phenylmercapto-m.-phenylmercapto sulfide p-phenylmercapto-m-phenylmercapto diphenyl sulfide o-bis(o-phenylmercaptophenylmercapto)benzene p-bis(p-phenylmercaptophenylmercapto)benzene p-bis(o-phenylmercaptophenylmercapto)benzene p-bis(m-phenylmercaptophenylmercapto)benzene m-bis(p-phenylmercaptophenylmercapto)benzene o-bis(p-phenylmercaptophenylmercapto)benzene and the like and mixtures thereof.

Illustrative of the mixed polyphenyl ether-thioether compounds which can be employed as base stocks in the compositions of this invention are for example,

o-phenylmercapto-m-phenoxy benzene p-phenylmercapto-o-phenoxy benzene m-phenoxy-p-phenylmercapto benzene o-phenylmercapto-p-phenoxydiphenyl sulfide o-phenylmercapto-m '-phenoxydiphenyl sulfide o-phenoxy-m-phenylmercaptodiphenyl sulfide m-phenoxy-p-phenylmercaptodiphenyl sulfide diphenyl o-phenoxy-p'-phenylmercaptodiphenyl sulfide p-phenoxy-p-ph'enylmercaptodiphenyl sulfide o-phenoxy-o'-phenylmercaptodiphenyl sulfide o,o-bis(phenylmercapto)diphenyl ether o-phenylmercapto-m-phenylmercaptodiphenyl ether o-phenylmercapto-p-phenylmercaptodiphenyl ether m-(m-phenylmercaptophenylmercapto)(mphenoxyphenylmercapto)benzene [m-(m-phenylmercaptophenylmercapto)phenyl][m- (m-phenoxyphenylmercapto)phenyl]sulfide 3-(m-phenylmercaptophenylmercapto)-3'-(mphenyl-mercaptophenoxy)diphenyl sulfide 3,3-bis(m-phenylmercaptophenylmercapto)diphenyl ether W 3-(m-phenylmercaptophenylmercapto)-3-(mphenoxyphenoxy)diphenyl sulfide 4-(m-phenylmercaptophenylmercapto)-4'-(mphenylmercaptophenoxy)diphenyl ether 3-(m-phenylmercaptophenylmercapto)-3'-(mphenoxy-phenylmercapto)diphenyl ether 4,4'-bis(m-phenylmercaptophenoxy)diphenyl sulfide 4,4'-bis(m-phenoxyphenylmercapto)diphenyl sulfide 3-(m-phenoxyphenylmercapto) 3'-(mphenylmercapto phenoxy)diphenyl sulfide 3,3-bis(m-phenylmercaptophenoxy)diphenyl ether 4-(m-phenylmercaptophenylmercapto,)-4'-(mphenoxyphenoxy)diphenyl ether 3-( p-phenylmercaptophenoxy )-,3 p-phenoxyphenoxy)-diphenyl sulfide 3-(m-phenylmercaptophenoxy) 3f-(mphenoxyphenylmercapto)diphenyl ether 3,3'-bis(m-phenoxyphenylmercapto)diphenyl ether and 3-(m-phenoxyphenylmercapto )-3 m-phenoxyphenoxy)-diphenyl sulfide In addition to the foregoing compounds, the phenyl and phenylene of such compounds can contain substitu ents, such as alkyl of one to four carbon atoms, alkoxy of one to four carbon atoms and halogen such as chlorine, bromine and fluorine. Examples of such compounds are as follows:

4,4'-bis(m-tolylmercapto)diphenyl ether 3,3'-bis(m-tolylmercapto)diphenyl ether 2,4-bis(m-tolylmercapto)diphenyl ether 3,4'-bis(m-tolylmercapto)diphenyl ether 3,3'-bis(p-tolylmercapto)diphenyl ether 3,3'-bis(xylylmercapto)diphenyl ether 4,4'-bis(xylylmercapto )diphenyl ether 3,4-bis(xylylmercapto)diphenyl ether 3,4-bis(m-isopropylphenylmercapto)diphenyl ether 3,3'-bis(m-isopropylphenylmercapto)diphenyl ether 2,4'-bis(m-isopropylphenylmercapto)diphenyl ether 3,4'-bis(p-tert-butylphenylmercapto)diphenyl ether 4,4'-bis(p-terhbutylphenylmercapto)diphenyl ether 3,3'-bis(p-tert-butylphenylmercapto)diphenyl ether 3,3-bis(2,4-di-tertbutylphenylmercapto)diphenyl ether 3,3'-bis(3-chlorophenylmercapto')diphenyl ether 4,4-bis( 3-chlorophenylmercapto )diphenyl ether 3,3' bis(m-trifluoromethylphenylmercapto)diphenyl ether 4,4'-bis(m-trifluoromethylphenylmercapto)diphenyl ether 3,4-bis(m-trifluoromethylphenylmercapto)diphenyl ether 2,3'-bis(m-trifluoromethylphenylmercapto)diphenyl ether 3 ,3i'-bis(p-trifluoromethylphenylmercapto)diphenyl ether 3,3'-bis(o-trifluoromethylphenylmercapto)diphenyl ether 3,3'-bis(m-methoxyphenylmercapto)diphenyl ether 3,4-bis(m-isopropoxyphenylmercapto)diphenyl ether 3,4'-bis(m-perfluorobutylphenylmercapto)diphenyl ether 2-(m-tolyloxy)-2'-phenylmercaptodiphenyl sulfide 2-(p-tolyloxy)-3-phenylmercaptodiphenyl sulfide 2-(o-tolyloxy)-4'-phenylmercaptodiphenyl sulfide 3-(m-tolyloxy)-3-phenylmercaptodiphenyl sulfide 3-(m-tolyloxy)-4'-phenylmercaptodiphenyl sulfide 4-(m-tolyloxy)-4-phenylmercaptodiphenyl sulfide 3-xylyloxy-4-phenylmercaptodiphenyl sulfide 3-xylyloxy-3 '-phenylmercaptodiphenyl sulfide 3-phenoxy-3'-(m-tolylmercapto)diphenyl sulfide 3-phenoxy-4'-(m-tolylmercapto)diphenyl sulfide 2-phenoxy-3'-(p-tolylmercapto)diphenyl sulfide 3-phenoxy-4'-(m-isopropylphenylmercapto)diphenyl sulfide 3-phenoxy-3 -(m-isopropylphenylmercapto )diphe- 3-m-toloxy-3 -(m-isopropylphenylmercapto )diphenyl sulfide 4-(m-trifluoromethylphenoxy)-4-phenylmercaptodiphenyl sulfide 3-(m-trifluoromethylphenoxy)-4-phenylmercaptodiphenyl sulfide 2-(m-trifluoromethylphenoxy)-3'-phenylmercaptodiphenyl sulfide 3-(m-trifluoromethylphenoxy)-3'-phenylmercaptodiphenyl sulfide 3-( p-chlorophenoxy )-3 -phenylmercaptodiphenyl 3 m-bromophenoxy )-4 '-phenylmercaptodiphenyl bis[m-(m-chlorophenoxy)phenyl]sulfide m-bis[3-(p-methylphenylmercapto)phenoxy]benzene m-bis[3-(m-trifluoromethylphenoxy)phenylmercaptolbenzene m-bis[3-(m-bromophenoxy)phenylmercapto]benzene 3 ,3 '-bis[rn-(p-methylphenylmercapto )phenoxy]- diphenyl sulfide 3,4-bis[rn-(p-methylphenylmercapto)phenoxy]- diphenyl sulfide 3-(p-xenyloxy)-3'-phenylmercapto diphenyl sulfide,

and the like and mixtures thereof. It is also contemplated within the scope of this invention to employ mixtures of polyphenyl ether-thioethers as base stocks.

The boron compounds useful in the compositions of this invention are well known to the art. The phenyl boric acids can be prepared in accordance with the procedure set forth in articles by R. M. Washburn, et al., Advances in Chemistry Series, 32, 208, (1961) or W. Gerrard, The Organic Chemistry of Boron, Academic Press, New Yor 59, (1961), or U. S. Pat. No. 3,092,652. The diphenylborinic acids can be prepared by acid hydrolysis of aminoethyl diphenylborinates by the process set forth in an article by R. L. Letsinger et al, J. Am. Chem. Soc., 77, 2491(1955).

The following examples serve to further illustrate the invention. All parts are parts by weight unless otherwise expressly set forth".

EXAMPLE Weight Percent meta-bis(phenylmercapto )benzene 50 bis(m-phenoxyphenyl )sulfide 12.5 (mphenoxyphenyl)( m-phenylmercaptophenyl)sulfide 23 .5 bis(m-phenylmercaptophenyl)sulfide l 2.65 3 ring and 5 ring thioethers 1.35

and containing 10 parts permillion of a dimethyl silicone antifoam agent (Dow-Corning 200, 350 cs. fluid). After stirring at 40C. to dissolve the acid, the mixture is cooled to room temperature and filtered. Lubricant compositions without boron additives were used as control.

The useful life of a functional fluid can be determined on the basis of many criteria such as the extent of viscosity increase (oxidative stability) and corrosiveness toward metals under the conditions of use. The major bench scale method used for evaluating the oxidative stability of a functional fluid is the procedure given in Federal Test Specification 791, Method 5308 according to which the lubricantcornposition is heated at a specified temperature in the'pr esence of certain metals and oxygen and the viscosity increase of the lubricant is determined.

The compositions of this example were tested according to the procedure of Federal Test Specification 791, Method 5308, Le, 500F. for 48 hours with 5 liters/hour of air in the presence of steel, copper, silver, titanium, magnesium alloy and aluminum alloy. Information with respect to corrosiveness of the compositions to metals was also obtained. However, only the results upon copper and silver are reported since all the compositions tested had essentially no effect on the other metals employed. Viscosity measurements were made according to ASTM Method D-44553T using a Cannon-Fenske modified Ostwald viscosimeter. The control base fluid ether and the compositions of this invention exhibited substantially the same viscosity increase. The corrosiveness to metals was determined by weighing metal specimens of known size before and after the test. Results and further details are given the Table below.

TABLE Metal Attack mg/cm Boron Additive Cu Ag none (control) 2.4 0.5 phenylboric acid 0.0 0. l 8 d-phenoxyphenylbon'c acid 0.05 0.17 3-fluorophenylboric acid 0.l8 0.06 4-bromophcnylboric acid 0.13 0.14 mixture of Z-nitrophenylboric acid and 4-nitrophenylboric acid 0.33 0.01 4-methylphenylboric acid 0.14 0.14

From the above it is clearly evident that the compositions of this invention exhibit markedly reduced corrosivity toward metals with no loss of oxidative stability and therefore have an extended useful life.

It will be appreciated that the compositions of the invention may also contain other additives, such as oxidation inhibitors, rust and corrosion inhibitors, antifoaming agents, detergents, viscosity index improvers such as polymeric materials for example, polyacrylate alkyl esters, polymethacrylate alkyl esters, polyoxyalkylene compounds, polyurethanes an and the like. Such additives are usually employed in amounts as low as 10 parts per million for antifoaming agent to as much as parts by weight of the total compositions for viscosity index improvers.

While the invention has been described with respect to specific examples and embodiments, it is to be understood that the invention is not limited thereto and that it can be variously practiced within the scope of the following claims.

The embodiments of this invention in which a particular property or privilege is claimed are defined as follows:

1. Composition consisting essentially of a major amount of base fluid selected from the group consisting of polyphenyl thioethers, polyphenyl ether-thioethers, and mixtures thereof, having the formula RY(R -Y ),,R wherein R is phenyl, alkyl-substituted phenyl wherein the alkyl is of not more than four carbon atoms, alkoxysubstituted phenyl wherein the alkoxy is of not more than four carbon atoms or halogenated phenyl wherein the halogen is bromine, fluorine or chlorine, R is phenylene, alkyl or alkoxy-substituted phenylene wherein the alkyl contains no more than four carbon atoms or halogenated phenylene wherein the halogen is fluorine, bromine or chlorine, and Y is selected from oxygen and sulfur but at least one of the Ys is sulfur and a is an integer having a value of l to 6 and a corrosion inhibiting amount of a boron compound of the formula wherein R is alkyl or not more than four carbon atoms. halogen selected from chlorine, bromine and fluorine, alkoxy of not more than four carbon atoms, haloalkyl of not more than four carbon atoms and 3 halogen atoms selected from chlorine, bromine and fluorine, haloalkoxy of not more than four carbon atoms and 3 halogen atoms selected from chlorine, bromine and fluorine, phenoxy, phenylmercapto or N0 R is halogen selected from chlorine, bromine and fluorine or alkyl of not more than four carbon atoms, nis an integer of 0 to 3, m is an integer of 0 to 2, x and y are integers from 1 to 2 and the sum of x and y is 3.

2. Composition of claim 1 wherein the boron compound is present in an amount from about 0.01 to about 1.5 percent by weight based on the weight of the total composition.

3. Composition of claim 1 wherein x is 2.

4. Composition of claim 1 wherein y is 2.

5. Composition of claim 1 wherein m is zero.

6. Composition of claim 1 wherein n is zero.

7. Composition of claim 1 wherein R is halogen and m is zero.

8. Composition of claim 1 wherein R is haloalkyl and m is zero.

9. Composition of claim 1 wherein R is alkyl and R is halogen.

l0. Composition of claim 1 wherein the boron compound is phenylboric acid.

11. Composition of claim 1 wherein the boron compound is 4-phenoxyphenylboric acid.

12. Composition of claim 1 wherein the boron compound is 3-fluorophenylboric acid.

l3. Composition of claim 1 wherein the boron compound is 4-bromophenylboric acid.

14. Composition of claim 1 wherein the boron compound is a mixture of Z-nitrophenylboric acid and 4- nitrophenylboric acid.

15. Composition of claim 1 wherein the boron compound is 4-methylphenylboric acid.

UNITED STATES PATENT OFFICE v CERTIFICATE OF CORRECTION Patent No. 2165.175 Dated Agggggt 2Q, 1913 Inventofls) Frank S. Clarkand Loren W. Bannister It is certifiedthat error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

T. Column 2, Formula at line 13, "Rfg should, be corrected to read R ---5 same column, line 3, "N0 should be corrected to read N0 e.

Column 3-, line 47, please delet H before n Same column, me lnei pl a arma?'Ipheny erc a to diphenyl" to read phenjrlmercapto diphenyl Column 7', claim l the second formula, "R should be 7 corrected to read I R m} a Signed and sealed this 22nd day of January 197L (SEAL) Attest: EDWARD M.FLETCHER,JR. RENE D. TEGTMETYER Attesting Officer Acting Commissioner of Patents Po-wso tmr rnt STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No- 2.js%.'175- I Dated August 28;. 197% Inventor(s) Frank s. Clark-and Loren w. Bannister It is certified-that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

r I II,

Column 2, Formula at line 13, R?

to read R m same column, line. corrected to read N0 shouldbe corrected 3, "No should be Column 3', n 7, please delete*"(" before "m-"; same ol mn, m;i..line ..2l ee.. 9 9r1 e 'fplzeny ercap diphenyl" to read phenylmercapto dipheny i a Column 7, claim 1 the second formula, "R v" should be corrected to r'ead .R v I Signed and sealed this 22nd dayof January-197A.

- (SEAL) Attest:

EDWARD M.FLETCHER,JR. RENE D. TEGTMEYER I Attesting Officer Acting Commissioner'of Patents 

2. Composition of claim 1 wherein the boron compound is present in an amount from about 0.01 to about 1.5 percent by weight based on the weight of the total composition.
 3. Composition of claim 1 wherein x is
 2. 4. Composition of claim 1 wherein y is
 2. 5. Composition of claim 1 wherein m is zero.
 6. Composition of claim 1 wherein n is zero.
 7. Composition of claim 1 wherein R is halogen and m is zero.
 8. Composition of claim 1 wherein R is haloalkyl and m is zero.
 9. Composition of claim 1 wherein R is alkyl and R1 is halogen.
 10. Composition of claim 1 wherein the boron compound is phenylboric acid.
 11. Composition of claim 1 wherein the boron compound is 4-phenoxyphenylboric acid.
 12. Composition of claim 1 wherein the boron compound is 3-fluorophenylboric acid.
 13. Composition of claim 1 wherein the boron compound is 4-bromophenylboric acid.
 14. Composition of claim 1 wherein the boron compound is a mixture of 2-nitrophenylboric acid and 4-nitrophenylboric acid.
 15. Composition of claim 1 wherein the boron compound is 4-methylphenylboric acid. 